Anthracene compounds and process of making them.



. To all whom it may concern:

compounds produced which contain thee-armation takes place, an acridonering being reaction is carried out, either one residue or UNITEDsTjA'rEs PATENT OFFICE.

max ALBERT mm; or MANNHEIM, GERMANY, ASSIGNOR T0 BADISCHE ANrLrN &

SODA FABRIK, or LUDWIGSHAFEN-ON THE-RHINE, GERMANY, A CORPORATION.

.ANTHRACENE COMPOUNDS AND PROCESS OF MAKING THEM.

No Drawing.

Be it known that I, MAx ALB RT KUNZ, Ph. D., chemist, citizen of theSwiss Republic, residing at Mannheim, Germany, have invented new anduseful Improvements in Anthracene Compounds and Processes of MakingThem, of which the following is a specification. v I

I have found that certain derivatives of dianthraquinonyl which containnegative substituents, namely one or more halogen atoms or nitro groups,can be condensed with salts, or esters, of amino-aryl-carboxylic acids,and that compounds "containing carboxy groups can be obtained. Accordingto the number of halogen atoms or nitro groups in the dianthraquinonylcompound and the conditions under which themore than one residue of theamino aryl carboxylic acid can be introduced. Those of thecarboxyaminodianthraquinonyl boxylic acid group in the ortiho positionto the nitrogen atom can be acted upon by suitable condensation agents,so that ring forformed, and if more than one such orthocarboxy residuehas been introduced into the dianthraquinonyl residue more than onecorresponding acridone ring can be produced. If the negativelysubstituted dianthraquinonyl compound which is used in carrying out theaforesaid process can undergo further ring formation, such [For instanceas is possible in the case of the formation of the pyranthrone complexfrom 2.2-dimethyl-1.1-dianthraquin onyl itself (see the specification ofBritish Patent No. 14,57 8 of 1905 (see also Bem'ohte der DeutschenOkemz'sck'en Ges ellschaft, vol. 43, p. 347), this ring formation can beeffected either Specification of Letters Patent.

before, or after, or at the same time as, the formation of the acridonering, according to the conditions under which the reaction is carriedout. If, in the production of the intermediate compounds, other thanorthocarboxylic' acid derivatives be employed,

Patented. Apr. 8, 1913. Application filed May20, 1911. Serial No.628,552.

only this ring formation, and not the acridone ring formation will takeplace.

In some cases, the two different ring formations can be effected at thesame time by the same condensation agent and in the cases where therings are formed one after the other, either the same'or a difi'erentcondensation agent can be employed. It is sometimes possible to effectthe condensation of the amino-aryl-carboxylic acid with thedianthraquinonyl compound and the further ringformatio'n in oneoperation.

After the ring formation has taken place, the products can be useddirectly as vat coloring matters, or they can be converted into theirsulfoacids and then be employed for dyeing wool.

The following examples will serve to illustrate how this invention canbe carried into practical effect, but my invention is not confined tothese examples. The parts are by weight,

Example '1: Boil together, for three hours, five parts of4.4-dichlor-2.2 -dimethyl-1.1-dianthraquinonyl, se'venty five partsofnitrobenzene, four parts of potassium anthranilate, and half a part ofcopper oxid. When the mixture is cold, filter off and wash the productwith alcohol, dilute acid, and water. The 4.4'-dianilido-2.2'dimethyl-Ll-dianthraquinonyl-dicarboxylic acid is easily soluble indilute alkali the solution being of a violet color, and by acid it isprecipitated from this solution in the form of violet colored flakes. Ityields an olive-green solution in concentrated sulfuric acid. It ispossible that the product of this example possesses a constitutioncorresponding to the formula Example 2: Boil together for thirty minutesforty parts of 2.4.2 .4-tetrabrom-1.1-

dianthraquinonyl, five hundred parts of nitrobenzene, twenty-two partsof potassium anthranilate, ten parts of calcined sothe formula i (I)HN/\ Example 3 :"Boil together, for thirty minutes, five parts ofnitro-2.2-dimethyl-1.1- dianthraquinonyl (obtainable by nitrating2.2-dimethyl-1.1-dianthraquinonyl in the cold with a mixture containingeighty-five per cent. of nitric acid and fifteen per cent. of sulfuricacid), one hundred parts of nitrobenzene, three and one-fifth parts ofpotassium anthranilate and five parts of potassium carbonate. Thendistil off the nitrobenzene' by means of steam and precipitate thecondensation product from the aqueous solution by means of hydrochloricacid. It consists when dry of a brownish black powder which is easilysoluble in dilute caustic soda solution with a brown color. Its solutionin concentrated sulfuric acid is reddish violet.

Example 4: Dissolve one part of2.2-

dimethyl 1.1 dianthraquinonyl LAX-diamth-ranilic acid in' from eight toten parts of ninety-seven per cent. sulfuric acid and heat the solutionon the water-bath until the said solution which was olive-green hasbecome deep red. This takes place after a few minutes heating. Afterabout a quarter of an hour, our the mixture on to ice and water, andlter it and wash the product until it is neutral. It is a violet coloredpowder which is diflicultly soluble in the usual organic solvents. Withalkaline hydrosulfite it yields a red vat which dyes cotton violetshades. It is possible that the product of this example has aconstitution corresponding to the formula Example 5: Introduce thirtyparts of 2.2- dimethyl -1.1- 'di anthraquinonyl-4.3.4.3-diphenylacridone (prepared according to the fore oing Example l) intoasolution of one hun red parts of caustic potash in eighty parts ofabsolute alcohol, while maintaining the temperature at from one hundredand thirty to one hundred and forty degrees centigrade. Then heat thewhole for one hour at from one hundred and forty-five to one hundred andfifty degrees centigrade. When the melt is cold, dissolve it in waterand blow air through the solution until the coloring matter isprecipitated. It is a dark brown-violet powder which yields a red vat inalkaline hydrosulfite, which vat colors cotton red shades which, uponwashing, are

converted into brown-violet shades. It is possible that the product ofthis example has a constitution corresponding to the formula NOW what Iclaim is I 1. The process of producing coloring mat-" quinonyl compoundwith a condensing agent.

3. The process of producing coloring matter of the anthracene series bytreating an ortho-carboxy-aryl-amino 2.2'- dimethyl-dianthraquinonylcompound with a condensing agent.

4; As new articles of manufacture the coloring matters of the anthraceneseries which can be obtained by treating anorthocarboxy-aryl-amino-dianthraquinonyl compound with a condensingagent, which coloring matters contain at least one acridone ring andconsist when dry of violet powders, are insoluble in water and in diluteacids and alkalis, but are soluble in concentrated sulfuric acid with areddish color, and in alkaline hydrosulfite forming reddish vats whichdye cotton from red to violet shades of excellent fastness.

5. As new articles of manufacture the coloring matters of the anthraceneseries which can be obtained by treating a carboxy-arylamino-2.2dimethyl-dianthraquinonyl compound with a condensing agent, whichcoloring matters contain both a pyranthrone complex and at least oneacridone ring, are insolubl in dilute acids and alkalis, but are solublein alkaline hydrosulfite yielding vats which dye cotton fast shades.

6. As a new article of manufacture the coloring matter of the anthraceneseries which can be obtained by treating 4.4'-diortho carboxy phenylamino 2.2'-dibron1 1.1'-dianthraquinonyl with a condensing agent, whichcoloring matter contains two acridone rings and consists when dry of adark brown-violet powder which is insoluble in dilute acids and alkalis,but which yields a red solution in concentrated sulfuric acid, and a redvat with alkaline hydrosulfite, which vat dyes cotton brown-violetshades -of excellent fa'stness.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses;

' MAX ALBERT KUNZ.

Witnesses:

J. ALEo. LLOYD,

A. O. TI'ITMANN.

